Triphosgene/Sodium Organosulfinate System: A General and Efficient Electrophilic Thiolation of Silylenol Ethers and Electron-Rich Heteroaromatics

Abstract

An efficient and practical approach to electrophilic thiolation was developed by using commercially available triphosgene as a reductant and the appropriate alkyl- or arylsulfinates, which were transformed in situ into electrophilic RSCl intermediates in the presence of triphosgene. This procedure represents a general and powerful approach for the synthesis of α-(trifluoromethyl)thio-substituted ketones and thiolated electron-rich heteroaromatic compounds.

Photocatalytic Perfluoroalkylation of Disulfides and Diselenides. Syntheses of Perfluoroalkyl Thio- and Seleno-ethers

“…Different approaches for synthesizing perfluoroalkylthiolated ethers [R­(Ar)-S-R F ] exist. Direct methods employ fluoroalkylthiolating reagents, − where both S and CF 3 /R F are introduced simultaneously into the organic scaffold, by either radical and polar substitution or addition reactions. , On the contrary, indirect syntheses of R­(Ar)-S-R F have been accomplished most often from sulfides and disulfides in the past (Scheme a–e). ,, Starting sulfur-containing substrates other than sulfides and disulfides have also been proposed for synthesizing perfluoroalkyl thio-ethers under photocatalytic and thermal methods. − However, these protocols require harsh reaction conditions and long reaction times.…”